CN103044465B - 一种稀土配位聚合物微片材料及其制备方法 - Google Patents
一种稀土配位聚合物微片材料及其制备方法 Download PDFInfo
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- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 74
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- 239000013256 coordination polymer Substances 0.000 title claims abstract description 39
- 229920001795 coordination polymer Polymers 0.000 title claims abstract description 39
- 150000002910 rare earth metals Chemical class 0.000 title claims abstract description 37
- 238000000034 method Methods 0.000 title claims abstract description 16
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims abstract description 57
- -1 rare earth ions Chemical class 0.000 claims abstract description 55
- 238000002360 preparation method Methods 0.000 claims abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 4
- ZGTMUACCHSMWAC-UHFFFAOYSA-L EDTA disodium salt (anhydrous) Chemical compound [Na+].[Na+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O ZGTMUACCHSMWAC-UHFFFAOYSA-L 0.000 claims abstract 6
- 229910002651 NO3 Inorganic materials 0.000 claims description 17
- 239000003109 Disodium ethylene diamine tetraacetate Substances 0.000 claims description 15
- 235000019301 disodium ethylene diamine tetraacetate Nutrition 0.000 claims description 15
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical group [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 claims description 11
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 9
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- 239000007864 aqueous solution Substances 0.000 claims description 6
- 239000013110 organic ligand Substances 0.000 claims description 6
- 229910052723 transition metal Inorganic materials 0.000 claims description 6
- 150000003624 transition metals Chemical class 0.000 claims description 6
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims description 5
- YJVUGDIORBKPLC-UHFFFAOYSA-N terbium(3+);trinitrate Chemical compound [Tb+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O YJVUGDIORBKPLC-UHFFFAOYSA-N 0.000 claims description 5
- 229910052684 Cerium Inorganic materials 0.000 claims description 4
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- MKNZSAIPAVSJSI-UHFFFAOYSA-N [Tb].S(O)(O)(=O)=O Chemical compound [Tb].S(O)(O)(=O)=O MKNZSAIPAVSJSI-UHFFFAOYSA-N 0.000 claims description 4
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- YBYGDBANBWOYIF-UHFFFAOYSA-N erbium(3+);trinitrate Chemical compound [Er+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O YBYGDBANBWOYIF-UHFFFAOYSA-N 0.000 claims description 4
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- GAGGCOKRLXYWIV-UHFFFAOYSA-N europium(3+);trinitrate Chemical compound [Eu+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GAGGCOKRLXYWIV-UHFFFAOYSA-N 0.000 claims description 4
- WLYAEQLCCOGBPV-UHFFFAOYSA-N europium;sulfuric acid Chemical compound [Eu].OS(O)(=O)=O WLYAEQLCCOGBPV-UHFFFAOYSA-N 0.000 claims description 4
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 claims description 4
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- MWFSXYMZCVAQCC-UHFFFAOYSA-N gadolinium(iii) nitrate Chemical compound [Gd+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O MWFSXYMZCVAQCC-UHFFFAOYSA-N 0.000 claims description 4
- 229910052746 lanthanum Inorganic materials 0.000 claims description 4
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 4
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical group [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims description 4
- VQEHIYWBGOJJDM-UHFFFAOYSA-H lanthanum(3+);trisulfate Chemical group [La+3].[La+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O VQEHIYWBGOJJDM-UHFFFAOYSA-H 0.000 claims description 4
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- CFYGEIAZMVFFDE-UHFFFAOYSA-N neodymium(3+);trinitrate Chemical compound [Nd+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O CFYGEIAZMVFFDE-UHFFFAOYSA-N 0.000 claims description 4
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Abstract
本发明涉及一种稀土配位聚合物微片材料及其制备方法,原料组分及其通式为Ln3(EDTA)3(OH)3·H2O,是用水热法使稀土离子与乙二胺四乙酸二钠盐配体通过自组装的方式首次合成稀土-乙二胺四乙酸配位聚合物微片材料。本发明所述的稀土配位聚合物是一种结晶性很好的晶体,该稀土配位聚合物具有微片状外观,微片厚度100~400纳米,微片粒度为1~5微米。本发明制备的稀土配位聚合物在负载特定金属离子后具有良好的荧光性能,可望作为荧光材料用于生物医药、光学存储、电子器件等领域。本发明制备过程简单、成本低、产量高、重复性好、快速、合成条件可控易、且合成产物结晶度高。
Description
技术领域
本发明是关于纳米材料,特别涉及一种采用水热法使稀土金属离子与乙二胺四乙酸配体自组装合成稀土-乙二胺四乙酸配位聚合物材料。
背景技术
金属离子-有机配体配位聚合物材料是一种新型配位聚物材料,具有独特的物理化学性能,在催化、非线性光学、气体储存及药物缓释领域有重要的应用(Moulton B,Zaworotko MJ,Curr Opin Solid State Mater Sci,2002,6:117~123;James S L,Chem Soc Rev,2003,32:276~288;Hong M C,Cryst Growth Des,2007,7:10~14)。
稀土由于因其独特的4f壳层电子结构,因此具有优良的光电磁物理特性,可作为优良的压电材料、热电材料、发光材料和磁性材料。有机配体乙二胺四乙酸是化学中一种良好的螯合剂,同时成本较低,可作为重金属解毒药、络合剂、抗氧增效剂、稳定剂及软化剂。因此将稀土和有机配体乙二胺四乙酸进行分子设计和合成,可结合稀土元素的优异物理性能和乙二胺四乙酸的生物相容性,制备出具有生物相容性和光学性能的稀土-乙二胺四乙酸配合物,可用于制备生物荧光探针、生物传感器和药物载体。
本发明技术首次利用无模板的水热合成法获得了一种稀土-乙二胺四乙酸配位聚合物微片材料,所制备的稀土配位聚合物具有微片状外观,产量高且分散性好。制备的稀土配位聚合物可具有良好的荧光性能,可作为荧光材料用于生物医药、光学存储、电子器件领域。
同时可充分利用该稀土配位聚合物掺杂过渡金属(例如:锰),有望获得优异的磁性性能,大大拓展了稀土配位聚合物材料的应用范围。
发明技术制备方法简单,快速,合成条件可控,且合成产物结晶度高。
发明内容
本发明的目的,在于提供一种稀土配位聚合物微片材料及其制备方法,本发明采用水热合成法,制备的配位聚合物的厚度可达纳米级,且制备过程简单、成本低、产量高、重复性好、快速、合成条件可控易、产物化学计量比合适且合成产物结晶度高。
本发明通过如下技术方案予以实现。
一种稀土配位聚合物微片材料,组分及其通式为Ln3(EDTA)3(OH)3·H2O,其中Ln为镧、铈、镨、钕、钐、铕、钆、铽、镝、铒或其中两种或两种以上元素的混合,EDTA为含两个去质子羧酸根的乙二胺四乙酸。
该稀土配位聚合物微片材料,是以一种或者两种及两种以上混合的稀土盐或者稀土氧化物为稀土金属离子来源,以乙二胺四乙酸二钠盐为有机配体来源;所述稀土盐为稀土硝酸盐、稀土硫酸盐;所述的稀土硝酸盐为硝酸镧、硝酸铈、硝酸镨、硝酸钕、硝酸钐、硝酸铕、硝酸钆、硝酸铽、硝酸镝、硝酸铒;所述的稀土硫酸盐为硫酸镧、硫酸铈、硫酸镨、硫酸钕、硫酸钐、硫酸铕、硫酸钆、硫酸铽、硫酸镝、硫酸铒;所述稀土氧化物为氧化镧、氧化铈、氧化镨、氧化钕、氧化钐、氧化铕、氧化钆、氧化铽、氧化镝、氧化铒。
该稀土配位聚合物微片材料,也可以掺杂过渡金属锰元素,例如硝酸锰。
所述稀土配位聚合物的形貌呈微片状,微片厚度可控制,可从纳米级到微米级,微片厚度分布范围为100~400纳米,粒度分布范围为1~5微米。
一种稀土配位聚合物微片材料的制备方法,具有如下步骤:
(1)一种稀土配位聚合物微片材料,原料组分及其通式为Ln3(EDTA)3(OH)3·H2O,其中Ln为镧、铈、镨、钕、钐、铕、钆、铽、镝、铒或其中两种或两种以上元素的混合,EDTA为含两个去质子羧酸根的乙二胺四乙酸。
该稀土配位聚合物微片材料,是以一种或者两种及两种以上混合的稀土盐或者稀土氧化物为稀土金属离子来源,以乙二胺四乙酸二钠盐为有机配体来源;所述稀土盐为稀土硝酸盐、稀土硫酸盐;所述的稀土硝酸盐为硝酸镧、硝酸铈、硝酸镨、硝酸钕、硝酸钐、硝酸铕、硝酸钆、硝酸铽、硝酸镝、硝酸铒;所述的稀土硫酸盐为硫酸镧、硫酸铈、硫酸镨、硫酸钕、硫酸钐、硫酸铕、硫酸钆、硫酸铽、硫酸镝、硫酸铒;所述稀土氧化物为氧化镧、氧化铈、氧化镨、氧化钕、氧化钐、氧化铕、氧化钆、氧化铽、氧化镝、氧化铒。
该稀土配位聚合物微片材料,也可以掺杂过渡金属锰元素,例如硝酸锰。
(2)将乙二胺四乙酸二钠盐溶解于去离子水中,乙二胺四乙酸二钠盐的浓度为0.42摩尔每升;
(3)将稀土金属离子源加入到步骤(2)的乙二胺四乙酸二钠盐的水溶液中,此过程不断搅拌溶解均匀,所述的稀土金属离子浓度范围为0.25~0.34摩尔每升;
(4)将步骤(3)得到的悬浊液移至高压反应釜中,密封;
(5)将高压反应釜中悬浊液于140~180℃反应2~100小时,洗涤,所得材料经过干燥,得到稀土配位聚合物微片材料。
所述步骤(5)的釜中悬浊液优选的反应温度为160℃,反应时间为24小时。
本发明有益效果是,首次利用无模板的水热合成法获得了一种稀土-乙二胺四乙酸配位聚合物微片材料,所制备的稀土配位聚合物具有微片状外观,产量高且分散性好;制备过程简单、成本低、产量高、重复性好、快速、合成条件可控且得到配合物产品结晶度高。本发明的稀土配位聚合物具有良好的荧光性能,可作为荧光材料用于生物医药、光学存储、电子器件领域。同时可充分利用该稀土配位聚合物掺杂过渡金属(例如:锰),有望可获得优异的荧光和磁性性能,大大拓展了稀土配位聚合物材料的应用范围。
附图说明
图1为实施例1制得的镧-乙二胺四乙酸配位物聚合材料的高倍扫描电镜图;
图2为实施例1制得的镧-乙二胺四乙酸配位物聚合材料的X射线衍射分析图谱;
图3为实施例5制得的铈-乙二胺四乙酸配位物聚合材料的高倍扫描电镜图;
图4为实施例6制得的镧-铽-乙二胺四乙酸配位物聚合材料的高倍扫描电镜图;
图5为实施例6制得的镧-锰-乙二胺四乙酸配位物聚合材料的高倍扫描电镜图;
图6为实施例7制得的镧-铽-乙二胺四乙酸配位物聚合材料的荧光光谱图。
具体实施方式
下面通过具体实施例对本发明做进一步描述。
实施例1
将0.42摩尔每升的乙二胺四乙酸二钠盐溶解于去离子水中,再将0.34摩尔每升的硝酸镧加入到上述乙二胺四乙酸二钠盐的水溶液中,搅拌溶解均匀后,将得到的悬浊液移至高压反应釜中,密封后,160℃反应24小时,洗涤,所得材料经过60℃干燥,即可得到微片状镧-乙二胺四乙酸配位聚合物。图1为本发明制得的镧-乙二胺四乙酸配位物聚合材料的高倍扫描电镜图。微片厚度分布范围为100~400纳米,微片粒度分布范围为1~5微米。图2为本发明制得的镧-乙二胺四乙酸配位物聚合材料的X射线衍射分析图谱。表明得到的稀土配位聚合物材料是一种结晶性很好的晶体。
实施例2
改变水热反应时间,将24小时改为2小时,将温度改为180℃,其它过程同实施例1,可制得微片状镧-乙二胺四乙酸配位聚合物。微片粒度为2~4微米,厚度为200~400nm。
实施例3
改变水热反应时间,将24小时改为100小时,将温度改为140℃,其它过程同实施例1,可制得微片状镧-乙二胺四乙酸配位聚合物。微片粒度为3~5微米,厚度为100~400nm。
实施例4
改变硝酸镧的浓度,将0.34摩尔每升改为0.25摩尔每升,其它过程同实施例1,可制得微片状镧-乙二胺四乙酸配位聚合物。微片粒度为2~5微米,厚度为100~400nm。
实施例5
改变稀土金属离子源,将硝酸镧换成硝酸铈加入到上述乙二胺四乙酸二钠盐的水溶液中,其它过程同实施例1,可制得微片状铈-乙二胺四乙酸配位聚合物。图3为本发明制得的铈-乙二胺四乙酸配位物聚合材料的高倍扫描电镜图。微片粒度为1~5微米。厚度为100~400纳米
实施例6
改变稀土金属离子源,将0.34摩尔每升硝酸镧换成0.32摩尔每升的硝酸镧和0.02摩尔每升的硝酸铽加入到上述乙二胺四乙酸二钠盐的水溶液中,其它过程同实施例1,可制得微片状镧-铽-乙二胺四乙酸配位聚合物。图4为本发明制得的镧-铽-乙二胺四乙酸配位物聚合材料的高倍扫描电镜图。该微片粒度为1~4微米,厚度为100~300纳米。该配位聚合物材料均具有较好荧光特性,如图5,镧-铽-乙二胺四乙酸配位聚合物的发射图谱在520纳米和535纳米处存在特征峰,表明配合物具有绿色荧光发射性能。
实施例7
改变金属离子源并掺杂锰,将0.34摩尔每升硝酸镧换成0.17摩尔每升的硝酸镧和0.17摩尔每升的硝酸锰加入到上述乙二胺四乙酸二钠盐的水溶液中,其它过程同实施例1,可制得微片状镧-锰-乙二胺四乙酸配位聚合物。图6为本发明制得的镧-锰-乙二胺四乙酸配位物聚合材料的高倍扫描电镜图。该微片粒度为1~2微米,厚度为100~200纳米。
以上仅在说明本发明的技术方案,对本发明的保护范围不构成任何限制,本发明所列举的各原料都能实现本发明。凡采用等同变换或是等效替换而形成的技术方案,均落在本发明权利保护范围之内。
Claims (4)
1.一种稀土配位聚合物微片材料,组分及其通式为Ln3(EDTA)3(OH)3·H2O,其中Ln为镧、铈、镨、钕、钐、铕、钆、铽、镝、铒或其中两种或两种以上元素的混合,EDTA为含两个去质子羧酸根的乙二胺四乙酸;
该稀土配位聚合物微片材料,是以一种或者两种及两种以上混合的稀土盐或者稀土氧化物为稀土金属离子来源,以乙二胺四乙酸二钠盐为有机配体来源;所述稀土盐为稀土硝酸盐、稀土硫酸盐;所述的稀土硝酸盐为硝酸镧、硝酸铈、硝酸镨、硝酸钕、硝酸钐、硝酸铕、硝酸钆、硝酸铽、硝酸镝、硝酸铒;所述的稀土硫酸盐为硫酸镧、硫酸铈、硫酸镨、硫酸钕、硫酸钐、硫酸铕、硫酸钆、硫酸铽、硫酸镝、硫酸铒;所述稀土氧化物为氧化镧、氧化铈、氧化镨、氧化钕、氧化钐、氧化铕、氧化钆、氧化铽、氧化镝、氧化铒;
该稀土配位聚合物微片材料,也可以掺杂过渡金属锰元素的硝酸锰。
2.根据权利要求1的一种稀土配位聚合物微片材料,其特征在于,所述稀土配位聚合物的形貌呈微片状,微片厚度可控制,可从纳米级到微米级,微片厚度分布范围为100~400纳米,粒度分布范围为1~5微米。
3.权利要求1的一种稀土配位聚合物微片材料的制备方法,具有如下步骤:
(1)一种稀土配位聚合物微片材料,原料组分及其通式为Ln3(EDTA)3(OH)3·H2O,其中Ln为镧、铈、镨、钕、钐、铕、钆、铽、镝、铒或其中两种或两种以上元素的混合,EDTA为含两个去质子羧酸根的乙二胺四乙酸;
该稀土配位聚合物微片材料,是以一种或者两种及两种以上混合的稀土盐或者稀土氧化物为稀土金属离子来源,以乙二胺四乙酸二钠盐为有机配体来源;所述稀土盐为稀土硝酸盐、稀土硫酸盐;所述的稀土硝酸盐为硝酸镧、硝酸铈、硝酸镨、硝酸钕、硝酸钐、硝酸铕、硝酸钆、硝酸铽、硝酸镝、硝酸铒;所述的稀土硫酸盐为硫酸镧、硫酸铈、硫酸镨、硫酸钕、硫酸钐、硫酸铕、硫酸钆、硫酸铽、硫酸镝、硫酸铒;所述稀土氧化物为氧化镧、氧化铈、氧化镨、氧化钕、氧化钐、氧化铕、氧化钆、氧化铽、氧化镝、氧化铒;
该稀土配位聚合物微片材料,也可以掺杂过渡金属锰元素的硝酸锰;
(2)将乙二胺四乙酸二钠盐溶解于去离子水中,乙二胺四乙酸二钠盐的浓度为0.42摩尔每升;
(3)将稀土金属离子源加入到步骤(2)的乙二胺四乙酸二钠盐的水溶液中,此过程不断搅拌溶解均匀,所述的稀土金属离子浓度范围为0.25~0.34摩尔每升;
(4)将步骤(3)得到的悬浊液移至高压反应釜中,密封;
(5)将高压反应釜中悬浊液于140~180℃反应2~100小时,洗涤,所得材料经过干燥,得到稀土配位聚合物微片材料。
4.根据权利要求3的一种稀土配位聚合物微片材料的制备方法,其特征在于,所述步骤(5)的釜中悬浊液优选的反应温度为160℃,反应时间为24小时。
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